Motor fuel composition



United States Patent 3,197,292 MOTOR FUEL COMPOSITIGN George W. Eckert and Alfred Arkell, Wappingers Falls,

N.Y., assignors to Texaco Inc, New York, N.Y., a corporation of Delaware No Drawing. Filed May 18, 1962, Ser. No. 195,959 9 Claims. (Cl. 44-69) This invention relates to a motor fuel composition containing a novel anti-knock additive. More particularly, the invention relates to a motor fuel for spark ignition internal combustion engines containing a salt of selenious acid and of a hydrocarbylamine as an anti knock agent.

Present day internal combustion engines have high compression ratios and require high octane fuels for satisfactory performance. This places a severe strain on petroleum refiners to produce fuels having the necessary high octane ratings demanded by these engines. The trend to higher compression ratios is continuing and it is estimated that motor fuels having octane ratings of the order of 105 and above will be required in the foreseeable future. At the present time, premium motor fuels having octane ratings of 97 or above are generally provided by relying heavily on refining operations such as fluid catalytic cracking, catalytic reforming, alkylation and isomerization, in conjunction with the use of a conventional anti-knock additive, such as a tetraalkyl lead compound. Frequently, these steps are not satisfactory to efficiently or economically produce a high octane motor fuel. As a result, many proposals have been made directed to fuel compositions containing additional additives, such as octane appreciators and the like, to supplement the anti-knock property of present day high performance motor fuels.

The subject invention involves the discovery that a gasoline or motor fuel can be substantially improved with respect to its anti-knock property by the addition of 0.01 to volume percent of a salt of selenious acid and of a hydrocarbylamine. Amine salts of selenious acid are true anti-knock agents as evidenced by the fact that they will substantially improve the octane ratings of a motor fuel in the absence of any other anti-knock additive.

The salts of selenious acid and of a hydrocarbylamine of this invention are represented by the following formula:

in which R represents a hydrocarbyl radical having from 3 to 28 carbon atoms, R and R" each represent a radical selected from the group consisting of hydrogen and radicals from the group consisting of (l) hydrocarbyl radicals having from 3 to 12 carbon atoms, (2) alkoxyhydrocarbyl radicals having from 5 to 12 carbon atoms, and

(3) aminohydrocarbyl radicals having from 3 to 12 carbon atoms, and x has a value from 1 to 2, and (b) compounds having the above noted formula in which R and R each interconnect to form with the basic nitrogen atom a heterocyclic ring selected from the group consisting of pyridine, pyrrolidine, piperidine, morpholine, quinoline, pyrrole and indole.

The anti-knock additives of this invention are prepared by mixing selenious acid with an amine as defined above. 1 to 2 moles of the amine are combined with 1 mole of selenious acid to form the salt of the invention although an excess of the amine over 2 moles can be employed to improve the solubility of the salt. However, it is preferred to combine the acid and the amine in 1:1 mole proportions. The hydrocarbyl radicals of the amine can be alkyl, aryl, alkaryl, ar-alkyl or alicyclic hydrocarbon radicals although it is preferred to employ the primary aliphatic amines and, in particular, the tertiary C C primary aliphatic amines.

3,197,292 Patented July 27, 1965 Examples of amines which can be employed include tertiarybutylamine, t-octylamine, oleylarnine, cyclohexylamine, dicyclohexylamine, dibutylarnine, tributylamine, di-Z-ethylhexylamine, tricaprylamine, aniline, N-methyl aniline, benzylamine, toluidine, xylidine, naphthylamine, pyridine, lutidine, quinoline, morpholine, piperidine, pyrrole, pyrrolidine, indole, Duomeen O, Duomeen T, propylenediamine, ethoxyethylamine, and the like. Particularly valuable amines for this invention are certain commercially available mixtures of tertiary alkylamine, such as Primene 81-R and Primene JMT. Primene 8l-R is a mixture of tertiary C to C primary aliphatic amines and Primene JM-T is a mixture of tertiary C to C primary aliphatic amines.

Outstandingly effective salts of the invention are those produced from the following mixtures:

1 mole selenious acidzl mole t-octylamine 1 mole selenious acidzl mole t-butylamine 1 mole selenious acid:2 moles t-octylamine 1 mole selenious acid:2 moles t-butylamine 1 mole selenious acidzl mole Primene 8l-.-R 1 mole selenious acid:2 moles Primene 81-R 1 mole selenious acidtl mole Primene J M -T 1 mole selenious acid:2 moles Primene JM-T The motor fuels of the invention consist of gasoline hydrocarbons and a minor amount sufiicient to impart an improved anti-knock property to the fuel of a salt. of selenious acid and of a hydrocarbylamine as described hereinabove. Generally, the additive salt will amount to about 0.01 to 5 volume percent of the fuel with amounts between about 0.10 and 2.0 volume percent being preferred. These fuels will generally contain aromatic and/or olefinic components in addition to the parafiins ordinarily present in a motor fuel; The aromatic and/ or olefin components can constitute as high as 100 percent of the fuel but usually will amount to between about 20 and volume percent. There are no critical requirements with respect to the proportions of the volatile hydrocarbon component types in the fuel.

A valuable feature of this invention is that organolead anti-knock agents can be employed simultaneously with the amine salt of selenious acid to produce a motor fuel composition having an unusually high octane rating. The organo-lead additives generally employed for antiknock purposes in motor fuels are the tetraalkyl lead compounds. Typical tetraalkyl lead anti-knock compounds are tetraethyl lead, tetramethyl lead, tetrabutyl lead, tetraamyl lead, tetrapropy'l lead, mixtures thereof and the like. The tetraethyl lead mixture commercially available for automotive use contains an ethylene bromide-ethylene chloride mixture as a scavenger for removing lead from the combustion chamber in the form of volatile lead halides, the latter two reagents being present in 1.0 theory and 0.5 theory respectively, theory denoting stoichiometric amount required for reaction with the lead content of the tetraethyl lead.

The organo-lead reagent is employed in motor fuel compositions in concentrations between 0.5 ml. per gallon up to the statutory limit of organo-lead reagent concentrations, which at the present time is 4 ml. per gallon for automotive fuel. The usual concentration of tetraethyl lead employed is between 1 and 3 ml. per gallon of gasoline.

The improvement in motor fuels containing a salt of selenious acid and of a hydrocarbylamine was demonstrated by incorporating measured amounts of these salts in various fuel compositions and determining the incremental increase in their R.O.N. (Research Octane No.). In these tests, the fuels designated as leaded fuels contained 3 ml. of tetraethyl lead while the unleaded fuel contained no tetraethyl lead but only the indicated amounts of the selenious acid: hydrocarbylamine salt of the invention. Four different fuels embracing a range of octane values were employed in this test.

Test Fuel A was a leaded regular grade gasoline boiling in the range from 104 F. to 418 F. and having an R.O.N. octane of 93.5. Test Fuel B was a leaded premium grade gasoline boiling in the range of 91 F. to 370 F. and having an R.O.N. value of 99.8. Test Fuel C was an unleaded platformate gasoline boiling in the range of 130 F. to 394 F. and having an R.O.N. value of 92.1. Test Fuel D was a leaded super premium grade gasoline boiling in the range of 92 F. to 382 F. and having an octane value of 105.

Various amounts of the additive salts of the invention were incorporated into these fuels and the incremental increase in R.O.N. value was determined. Results of these tests are tabulated in Tables I and II below.

Table I.Octane efiect of l :1 mole ratio amine salts of selenious acid and Primene JM-T Volume percent of Additive Research A R.O.N.

Table II.Octane effect of .1 :1 mole ratio of amine salts of selenious acid and Primene 81R The foregoing data demonstrates that selenious acidhydrocarbylamine salts very substantially improve the anti-knock rating of various motor fuel compositions including both conventionally leaded and unleaded gasolines.

We claim: V

1. A motor fuel in the gasoline boiling range containing an effective anti-knock amount of a salt of selenious acid and of a hydrocarbylamine having the formula: (a) H SeO (RNR'R") in which R represents a hydrocarbyl radical having from 3 to 28 carbon atoms, R and R each represent a radical selected from the group consisting of hydrogen and radicals from the group consisting of (l) hydrocarbyl radicals having from 3 to 12 carbon atoms, (2) alkoxyhydrocarbyl radicals having from 5 to 12 carbon atoms, and (3) aminohydrocarbyl radicals having from 3 to 12 carbon atoms, and x has a value from 1 to 2, and (b) compounds having the above noted formula in which R and R each interconnect to form with the basic nitrogen atom a heterocyclic ring selected from the group consisting of pyridine, pyrrolidine, piperidine, morpholine, quinoline, pyrrole and indole.

2. A motor fuel according to claim 1 in which said salt amounts to 0.01 to 5 volume percent of said fuel.

3. A motor fuel according to claim 1 in which said hydrocarbylamine is a tertiary C -C primary aliphatic amine.

A motor. fuel in the gasoline boiling range containing 0.01 to 5 volume percent of a salt consisting of a mole of selenious acid and a mole of PC alkyl pri mary amine.

5. A motor fuel in the gasoline boiling range containing 0.01 to 5 volume percent of a salt consisting of a mole of selenious acid and a mole of PC alkyl primary amine.

6. A motor fuel in the gasoline boiling range containing an effective anti-knock amount of an organo-lead compound and 0.01 to 5 volume percent of a salt of selenious acid and a hydrocarbylamine having the formula:

in which R represents a hydrocarbyl radical having from 3 to 28 carbon atoms, R and R" each represent a radical selected from the group consisting of hydrogen and radicals from the group consisting of (1) hydrocarbyl radicals having from 3 to 12 carbon atoms, (2) alkoxyhydrocarbyl radicals having from 5 to 12 carbon atoms, and (3) aminohydrocarbyl radicals having from 3 to 12 carbon atoms, and x has a value from 1 to 2, and (b) compounds having the above noted formula in which R and R each interconnect to form with the basic nitrogen atom a heterocyclic ring selected from the group consisting of pyridine, pyrrolidine, piperidine, morpholine, quinoline, pyrrole and indole.

'7. A motor fuel according to claim 6 in which said organo-lead compound is tetraethyl lead.

8. A motor fuel according to claim 6 in which said salt consists of a mole of selenious acid and a mole of t-C alkyl primary amine.

9. A motor fuel according to claim 6 in which said salt consists of a mole of selenious acid and a mole of PC alkyl primary amine.

References Cited by the Examiner UNITED STATES PATENTS 1,575,436 3/26 Midgley 44--76 1,906,724 5/33 Rosenstein et al 44-76 1,920,766 8/33 Rosenstein et al 4476 2,151,432 3/39 Lyons et a1 44-69 DANIEL E. WYMAN, Primary Examiner. 

1. A MOTOR FUEL IN THE GASOLINE BOILING RANGE CONTAINING AN EFFECTIVE ANTI-KNOCK AMOUNT OF A SALT OF SELENIOUS ACID AND OF A HYDROCARBYLAMINE HAVING THE FORMULA: 